Article https://doi.org/10.

1038/s41467-023-39192-z

Resolving nanostructure and chemistry of

solid-electrolyte interphase on lithium
anodes by depth-sensitive plasmon-
enhanced Raman spectroscopy

Received: 22 December 2022 Yu Gu 1,5, En-Ming You 1,5, Jian-De Lin1, Jun-Hao Wang1, Si-Heng Luo1,
Ru-Yu Zhou1, Chen-Jie Zhang2, Jian-Lin Yao2, Hui-Yang Li1, Gen Li 1,
Accepted: 31 May 2023
Wei-Wei Wang1, Yu Qiao 1, Jia-Wei Yan 1, De-Yin Wu 1, Guo-Kun Liu3,
1234567890():,;
1234567890():,;

Li Zhang1, Jian-Feng Li 1, Rong Xu4, Zhong-Qun Tian 1 , Yi Cui 4 &

Bing-Wei Mao1
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The solid-electrolyte interphase (SEI) plays crucial roles for the reversible
operation of lithium metal batteries. However, fundamental understanding of
the mechanisms of SEI formation and evolution is still limited. Herein, we
develop a depth-sensitive plasmon-enhanced Raman spectroscopy (DS-PERS)
method to enable in-situ and nondestructive characterization of the nanos-
tructure and chemistry of SEI, based on synergistic enhancements of localized
surface plasmons from nanostructured Cu, shell-isolated Au nanoparticles and
Li deposits at different depths. We monitor the sequential formation of SEI in
both ether-based and carbonate-based dual-salt electrolytes on a Cu current
collector and then on freshly deposited Li, with dramatic chemical recon-
struction. The molecular-level insights from the DS-PERS study unravel the
profound influences of Li in modifying SEI formation and in turn the roles of
SEI in regulating the Li-ion desolvation and the subsequent Li deposition at SEI-
coupled interfaces. Last, we develop a cycling protocol that promotes a
favorable direct SEI formation route, which significantly enhances the per-
formance of anode-free Li metal batteries.

Lithium metal is regarded as an ideal anode for rechargeable Li batteries
because of its ultrahigh specific capacity1–3. However, the electro-
chemical plating/stripping of Li metal usually presents a dendritic
morphology, leading to low Coulombic efficiency and poor cycling
stability of the Li metal anode4–6. The solid-electrolyte interphase (SEI), a
nanometer-thin layer formed at the electrode-electrolyte interface due
to the electrolyte decomposition, plays a crucial role in determining the
Li deposition/dissolution and thus the reversible operation of Li metal
batteries7,8. However, fundamental understanding of the SEI formation
and evolution during battery operation is still limited, which limits the
development of high-performance Li metal batteries.
The SEIs formed during the battery operation usually present
structural and compositional heterogeneity – nanometric phases
of decomposition products from the electrolyte are dynamically

1
State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian
Province (IKKEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. 2College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Suzhou, China. 3State Key Laboratory of Marine Environmental Science, College of the Environment and Ecology,
Xiamen University, Xiamen, China. 4Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA. 5These authors contributed
equally: Yu Gu, En-Ming You. e-mail: zqtian@xmu.edu.cn; yicui@stanford.edu; bwmao@xmu.edu.cn

Nature Communications | (2023)14:3536 1

Article https://doi.org/10.1038/s41467-023-39192-z

precipitated and distributed heterogeneously in the SEI7,9. The for-
mation and evolution of SEIs become more elusive when the anode-
free configuration of Li metal batteries is employed10–13, in which SEI
with different components and structures needs to form sequentially
on the surface of the Cu current collector and then on the deposited
Li14–16. Although SEIs have been intensively investigated by various
advanced experimental techniques17–26 and theoretical simulations27,28,
the preceding SEI formation on the Cu in the anode-free configuration
and its possible detrimental effects on Li deposition-dissolution
cycling stability is often overlooked. Therefore, in-situ methods that
can follow dynamic interfacial processes and provide accurate
molecular-level information is urgently needed to gain more detailed
insights into the complicated interfacial processes involving SEI for-
mation and evolution and to guide the design of favorable SEIs to
improve the performance of Li metal batteries.
Surface-enhanced Raman spectroscopy (SERS) is a surface-
sensitive technique based on the effect of localized surface plasmons
(LSPs) of especially free-electron metal (e.g., Au, Ag, Cu and Li)
nanostructures29–31. It is able to characterize the interfacial processes
with molecular-level fingerprint information over a wide spectral
range32–35, thereby showing great potential to identify the composition
and structure of SEIs in batteries36–43. However, since the LSP
enhancement exhibit an exponential decay of electromagnetic inten-
sity within a couple of nanometres32, its application in characterizing
the SEI with a thickness of tens of nanometers is limited – only the
information from the vicinity of hotspots with the large local electro-
magnetic field can be extracted by SERS (see Supplementary Note 1).
Alternatively, shell-isolated nanoparticle-enhanced Raman spectro-
scopy (SHINERS) is developed, in which plasmonic metal cores are
coated with ultrathin inert shells to separate the cores from the sub-
strate and are used solely as Raman signal amplifiers, giving reliable
signals from the sample surface44–51. Monitoring of dynamic nature of
SEI formation on anodes in Li-ion batteries via SHINERS has been
reported, including a recent study involving Si anodes52. However,
using the SHINERS to characterize the SEIs in Li metal batteries has
rarely been reported53, mainly due to the complex operation of SHI-
NERS at the highly reactive Li metal surfaces and in organic electrolytes.
In this work, we develop a depth-sensitive plasmon-enhanced
Raman spectroscopy (DS-PERS) method that combines the SERS and
SHINERS to in-situ characterize the dynamic processes of SEI forma-
tion and evolution during the operation of Li metal batteries. The
synergistic plasmonic enhancement of nanostructured Cu, shell-
isolated Au nanoparticles, and Li deposits enables a depth-sensitive
detection of signals from the SEI with a thickness of tens of nanometers
and its interfaces to electrode (Cu or Li) and electrolyte (Fig. 1a). We
further elucidate the formation of SEIs through two different routes,
the sequential formation and the direct formation, highly depending
on the cycling protocol. This comprehensive molecular-level infor-
mation from the DS-PERS enriches our understanding of SEI formation
and evolution during Li plating. Based on this understanding, we fur-
ther design the favorable SEIs for practical anode-free Li metal using a
potentiostatic-galvanostatic polarization strategy. The electrodes
engineered with this type of SEI exhibited significantly enhanced
cycling stability and an expanded lifetime in the anode-free Li metal
batteries. The DS-PERS method provides tremendous opportunities
for nondestructively characterizing the nanoscale interphases/inter-
faces with spatial information, which is a great challenge not only in the
battery field but also in the general fields of material sciences and
energy sciences.
Results and Discussion
Working principle of DS-PERS
The DS-PERS is based on a SERS-SHINERS integrated plasmonic
enhancement structure with unique depth sensitivity by employing a
SERS-active nanostructured Cu substrate, and shell-isolated nano-
particles (SHINs) introduced initially on top of the Cu substrate sur-
face, as illustrated in Fig. 1a and Supplementary Notes 2–5. The SHINs
had plasmonic Au cores (~60 nm) with ultrathin and pinhole-free SiO2
shells (~2 nm), and the nanostructured Cu was created by the elec-
trochemical oxidation-reduction roughening method54 (Supplemen-
tary Figs. 1, 2). Before Li deposition, the junctions of adjacent
nanostructured Cu serve as hotspots for providing the finger-print
information of SEI formed in the vicinity of Cu surface (i.e., the inner
region of SEI) in the early stage of formation (Fig. 1b). The LSPs-active
SHINs provide additional signals from the hotspots of the SHINs and
Cu such that the chemical and structural information of SEIs at outer
regions can be obtained (Fig. 1c). After Li deposition, the Li metal with
SHINs generated new hotspots (Fig. 1d) to further enhance Raman

a b SEI formation c SEI further growth d SEI restructuring

Electrolyte Laser
Raman
hotspot signals

III' III'
III III III III III III SEI
SHIN SEI
II' II'
II II SEI II II II II Li II' II'
II II II II II II I'
I I I

Cu Cu Cu Cu

e
Electrolyte
SiO2 shell Outer signals (by II & III) Outer signals (by II' & III')
Inner signals
Au Au + +
core core (excited by I & II) Inner signals (by I & II) Inner signals (by I' & II')
SEI Au
core
Li Li Outer layer Outer layer
Cu Cu Inner layer
Li Li Inner layer Inner layer
Li
0 10
log(Eloc/E0)4 Cu Cu Cu

Fig. 1 | DS-PERS by synergistic LSP enhancement pertinent to SEIs. from the SEI. e The distribution of simulated electromagnetic field near the inte-
a–d Schematics of the DS-PERS that enables detection of the signals from different grated plasmonic substrates during Li deposition. E1oc and E0 represent the loca-
depths in the SEI. The plasmonic structure of nanostructured Cu, SHINs and lized field and the incident field, respectively. Scale bar: 60 nm.
deposited Li generates strong electromagnetic field to enhance the Raman signals

Nature Communications | (2023)14:3536 2

Article https://doi.org/10.1038/s41467-023-39192-z

a 30 cps

Bulk electrolyte
b 30 cps

Bulk electrolyte


×0.025 ×0.025

Cu Cu + SHINs
~400 ~540
~1340 ~1540
1.2 V I+II 1.2 V
~400 ~540 ~1540 ~1190
Intensity (a.u.)

Intensity (a.u.)
I 0.8 V II+III 0.8 V
~700

I 0.2 V III 0.2 V

Cu@Li ~1050 Cu@Li + SHINs

~1050
~640
~380 1850
~920
I' 0.1 V I'+II' 0.1 V
~530
I' 0.2 V II'+III' 0.2 V

300 600 900 1200 1500 1800 300 600 900 1200 1500 1800
Raman shift (cm1) Raman shift (cm1)

c
Depth-fixed detection vs. Depth-sensitive detection
Cu-SEI Li-SEI Cu-SEI Li-SEI
Outer layer III III III' III'
Inner layer SEI restructuration
Li II II Li II' II'
Li II II II' II' Li
plating I' plating I'
I I
Cu Cu Cu Cu

ROLi, Li2NSO2CF3, Li3N LiOH, LiF, Li2SxOy, Li2O, Li2CO3 Li2SxOy, LiF, Li3N, ROLi LiF, Li2S, Li2O, Li3N

Fig. 2 | Characterizations of SEI formed in the 1 M LiTFSI in DME-DOL using DS-
PERS. a, b In-situ Raman spectra showing the sequential formation and evolution of
SEIs on the nanostructured Cu substrate (a) and the Cu-SHINs substrates (b) before
and after Li deposition. Raman spectra of the bulk electrolyte are displayed for
comparison. Peaks marked by asterisks are from the electrolyte. c Schematic
comparison of the depth-fixed strategy based on LSPs of Cu alone and the depth-
sensitive strategy based on synergetic LSPs of integrated Cu-SHINs for in-situ
probing the formation and restructuring of SEI. By the DS-PERS, it is revealed that
the primary Cu-SEI can undergo restructuring with the participation of freshly
deposited metallic Li to form low-oxidation-state species with highly amorphous
and heterogeneous structure.

signals of SEI near the Li surface and in the outer region by plasmonic
coupling. The key advantage of such an elaborative design is the
synergistic plasmonic enhancement effect, which provides higher
detection sensitivity and depth sensitivity of Raman signals from SEIs
and related interfaces. In this circumstance, we can capture the depth-
dependent nanostructure and chemistry of SEI during its formation
and evolution at different stages of Li plating.
The synergetic LSP enhancement was modeled using the finite
element method (Fig. 1e and Supplementary Figs. 2–4 and Supple-
mentary Table 1). For the Cu-SHINs integrated substrate (Supple-
mentary Note 3 and Supplementary Fig. 3), the hotspots were formed
in three types of junctions, namely, Cu island-to-Cu island (type-I), Cu
island-to-SHIN (type-II) and SHIN-to-SHIN (type-III) junctions. The
enhancement factor (EF) of such a configuration can reach up to 1010
(Supplementary Table 1), sufficiently high for the ultrasensitive
detection of the Raman signals from the SEI. However, the distribu-
tion of SHINs on the Cu surface changed after primary SEI formation
and Li deposition (Supplementary Fig. 4), and we need to consider
how the change of SHINs locations influenced the EF. First, SEI for-
mation was initiated only at the metal surface, leaving SHINs at least
partially embedded in the SEI (Supplementary Note 4). However,
since SEI components absorb light weakly and their dielectric con-
stants are close to the electrolyte, the SEI growth will not sub-
stantially decrease the strength of the electromagnetic field from the
plasmonic substrates (Supplementary Note 4). Even when the SHINs
were entirely embedded in the SEI, the average EF was still as high as
1010 (Supplementary Figs. 5, 6 and Supplementary Table 1). Second,
two SHINs locations, on top of and within the Li deposit, were
observed upon Li deposition. Only the SHINs on the Li deposits could
generate effective hotspots to maintain a high EF of up to 1010
(Supplementary Note 5 and Supplementary Fig. 7). The above pro-
posed plasmonic enhancement strategy with multiple hotspots
provides a basis for the sensitive detection of Raman signals of the
SEI during its formation.
To validate the synergetic LSP enhancement, we first performed
the in-situ Raman measurements on the Cu electrode in an ether-based
electrolyte of 1 M lithium bis(trifluoromethanesulfonyl)imide in 1,3-
dioxolane and 1,2-dimethoxyethane (LiTFSI in DME-DOL)1,55. The Cu
working electrodes with and without SHINs were assembled in a sealed
three-electrode Raman cell where Li foils served as both the reference
and counter electrodes (Supplementary Fig. 8a). A thin liquid layer
(< 100 μm) was trapped between the Cu surface and quartz window to
ensure that the Raman signals were from the metal-SEI interface,
instead of the bulk electrolyte (Supplementary Fig. 8b). This was
confirmed by the potential-dependent inversion of the intensity ratio
of two prominent bands at 743 and 942 cm−1, which are from the
vibration modes of the TFSI anion (S–N and C–S stretching, CF3
bending) and DOL solvent (C–O and C–C stretching), respectively
(Fig. 2a, b, and Supplementary Figs. 11, 12).
We then conducted the potential-dependent Raman measure-
ments to investigate the electrolyte reduction on a nanostructured Cu
substrate (Fig. 2a and Supplementary Fig. 11). In the first cycle from 2.0

Nature Communications | (2023)14:3536 3

Article
to 0.2 V without Li overpotential deposition (OPD), the cyclic voltam-
mograms (CVs) of the Cu electrode show two successive cathodic
waves starting from ~1.6 V (Supplementary Fig. 10) due to the solvent
reduction and anion reduction, respectively56. However, the bands at
~400, ~540 and ~1540 cm−1 for the reduction products of LiOH/LiF/
Li2SxOy, ROLi/Li2O and Li2CO3/ROCO2Li (Supplementary Table 2),
respectively, were not observed until the potential reached 1.0 V. The
spectra remained the same upon a further decrease of potential to
0.2 V (Fig. 2a and Supplementary Fig. 11), even with SEI continual
growth on the Cu surface. It means that Cu alone, due to the limited
detection sensitivity of hotspot I, can be used only to probe the fin-
gerprint information of the inner region of the SEI during its initial
formation (Fig. 2c). Notably, bands for electrolyte components at the
metal-electrolyte interface were still present even after the potential
decreased to 0 V (Supplementary Fig. 11), likely due to a small number
of electrolyte molecules buried in the SEI, which was recently observed
by Cui and coworkers57.
When the SHINs were integrated into the nanostructured
Cu substrate (Fig. 2b and Supplementary Fig. 12), the Raman bands
associated with the electrolyte reduction appeared as early as 1.4 V
(Supplementary Fig. 12), indicating the higher detection sensitivity of
the Cu-SHINs substrate with multiple hotspots (hotspots I and II).
When the potential is lower than 1.2 V, new bands at 1340, 1191, and
700 cm−1 (excited by hotspots II and III) appeared sequentially (Fig. 2b
and Supplementary Fig. 12), which were attributed to the formation of
ROLi/Li2SxOy, Li2NSO2CF3/Li2SxOy and Li3N, respectively, from the
successive reductions of TFSI and DOL (Supplementary Table 2). It
verified that the synergistic LSPR enhancement from the integrated
Cu-SHINs substrate enabled Raman signals to be detected from dif-
ferent depths of the SEI during its formation. Since the SHINs were
initially located on the top of the Cu surface and later presented in the
outer region of the growing SEI, this observation serves as convincing
evidence for the outer surface growth mechanism of SEI (Fig. 2c).
Pronounced changes in Raman spectra were observed on both the
nanostructured Cu and integrated Cu-SHINs substrates during a
negative potential excursion to −0.1 V where the Li OPD took place
(lower panels in Fig. 2a, b). The Raman bands of SEI species observed at
the positive potential disappeared, while strong and broad bands
overlapped in some specific regions for the SEIs formed on the Cu
substrate and over the entire wavenumber range for the SEIs formed
on the integrated Cu-SHINs substrate. These phenomena suggest that
the SEI was undergoing reconstruction with the participation of freshly
deposited Li (Supplementary Note 6). The largely broadened shape of
the vibrational bands indicates that the SEI on the Li surface is highly
amorphous and heterogeneous. Upon further Li deposition, significant
changes in the Raman spectra were observed only for the SEI on the
Cu-SHINs substrate (lower panels in Fig. 2a, b), again demonstrating
that the synergistic plasmonic substrates can create significant Raman
signal enhancement and thus enable depth-sensitive detection of SEI.
To study the reconstruction of SEI during Li deposition, we con-
ducted the in-situ Raman measurements using precise control of
applied potential at an interval of 5 mV (Supplementary Fig. 13). The
resulting broad bands were deconvoluted for component analysis
(Supplementary Fig. 14 and Supplementary Table 3). Prior to Li OPD,
the SEI formed on the Cu surface displayed a typical organic-inorganic
hybrid structure, in which high- and low-oxidation-state species (e.g.,
ROLi, Li2SxOy and LiF) were the major components of the SEI. However,
after the Li OPD was initiated, both the inner and outer regions of the
SEI underwent reconstruction with higher-oxidation-state species
decomposed to lower-oxidation-state species (e.g., Li2O, LiF, Li2S and
Li3N). The component analysis was supported by XPS profile analysis
(Supplementary Fig. 15). We expect that the role of metallic Li is to
promote additional chemical reactions to significantly alter the struc-
ture of the primary SEI on the Cu current collector to the final SEIs on
the deposited Li (Supplementary Note 6 and Supplementary Fig. 16).
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
Such a sequential formation and reconstruction of SEIs are overlooked
in the past research on Li metal batteries.
Sequential and direct formation of SEIs in carbonate-based
electrolytes
The DS-PERS method was then used to study the formation and evo-
lution of SEIs in a complex yet promising carbonate-based dual-salt
electrolyte of lithium difluoro(oxalato)borate and lithium tetra-
fluoroborate in diethyl carbonate and fluoroethylene carbonate
(LiDFOB-LiBF4/DEC-FEC) proposed by Dahn and coworkers58,59. We
apply a galvanostatic polarization (denoted as the G route) to a Cu | |Li
half-cell, where an integrated Cu-SHINs plasmonic substrate was used
as the working electrode. The resulting potential profiles and time-
dependent Raman spectra were recorded simultaneously in Fig. 3a, b.
As shown in Fig. 3a (black line), the potential on the Cu electrode
was decreased to around 0 V within the first 100 s, during which the
electrolyte was reduced to the primary SEI on Cu (denoted as Cu-SEI)
without the participation of Li OPD. In the corresponding Raman
spectra (Fig. 3b and Supplementary Fig. 18), broad background-like
features in the regions of 300–600 cm−1 and 1200–1600 cm−1 gradually
appeared due to the B-containing decomposition products of LiDFOB
salt and the carbonyl species from the reduction of DEC-FEC solvents
(Supplementary Table 4). At ~90 s, a new band at ~1011 cm−1 appeared
from the B–O/C–O stretching modes of B-containing components
(Supplementary Fig. 18), implying that the primary SEI formed on the
Cu surface was organic-rich.
As the polarization continued, the potential of the Cu electrode
became slightly lower than 0 V, implying the occurrence of Li OPD
(Fig. 3a, red line). Accordingly, dramatic changes in the Raman spectra
were observed: bands initially seen when the potential is above 0 V
disappeared, while four new broad bands associated with organic
B-containing species (at ~370 and ~540 cm−1) and Li carbonates/alk-
oxides (at ~1300 and ~1490 cm−1) appeared (Fig. 3b, Supplementary
Fig. 18 and Supplementary Table 4). These species were distributed
successively from the inner to outer regions of the SEI, as evidenced by
comparative Raman spectra recorded on the Cu-SHINs and bare
nanostructured Cu substrates (Supplementary Fig. 19). The intensities
of these bands continued to increase over time until after 30 min,
indicating that the SEI formation was completed. Deconvolution ana-
lysis (Supplementary Fig. 23 and Supplementary Table 4) suggested
that the final SEI was enriched by a mixture of organic and inorganic
species (e.g., B–F compounds and Li2CO3) throughout the thickness of
the SEI. Some of the mixture species were still in high-oxidation states.
We conclude that under the galvanostatic polarization, the SEI was
sequentially formed by electrolyte reduction at above 0 V (prior to Li
OPD), and followed by further electrolyte reduction below 0 V (with Li
OPD). This transition from the primary SEI on the Cu current collector
(i.e., Cu-SEI) to the final SEI on the Li (i.e., Li-SEI) was accompanied by a
significant chemical reconstruction, as schematically shown in Fig. 3c.
The composition and structure of the final Li-SEI were closely
related to the potential of electrolyte reduction. We found that
prolonging the bias at the potential prior to Li OPD can promote
the enrichment of high-oxidation-state organic components of the
final SEI, especially in the outer region, as confirmed by potential-
dependent Raman measurements (Supplementary Fig. 20 and Sup-
plementary Table 5). However, when the potential was decreased
rapidly to below 0 V, the formation of the primary Cu-SEI was sup-
pressed, leading to the direct formation of the SEI on the Li. Herein, we
design an electrochemically engineered strategy with a potentiostatic-
galvanostatic polarization (P-G route) to artificially construct a favor-
able SEI. The P-G route initiate with a negative potentiostatic stepping
(−0.1 V for 100 s, blue region in Fig. 3d) to incur the Li OPD and elec-
trolyte reduction for a certain time, followed by a galvanostatic plating
(~0.5 mA cm−2, purple region in Fig. 3d) to stabilized SEI formation.
Broad Raman bands characteristic of Li-SEI appeared immediately
4
Article
Fig. 3 | Formation and evolution of SEIs in the dual-salt electrolyte revealed by
DS-PERS. a–c E–t curve of the galvanostatic polarization (denoted as the G route)
of Li plating on Cu (a). In-situ Raman spectra recorded during the formation and
evolution of the SEI under the G route (b). Peaks marked by asterisks are from the
electrolyte. Schematics of the structure and chemistry of the SEI formed under the
G route (c). d, e j–t and E–t curves of electrochemically engineered potentiostatic-
galvanostatic polarization (denoted as the P-G route) of Li plating on Cu (d). In-situ
upon the cathodic potential stepping due to the absence of Cu-SEI
(Fig. 3e and Supplementary Figs. 21, 22). During the following galva-
nostatic plating, the intensities of the broad bands increased markedly
and approached saturation after only ~15 min, indicating faster evolu-
tion of SEI than the G route. Importantly, the chemistry and structure
of the SEI were significantly different from the sequentially formed SEI
under the G route (Fig. 3f), as further revealed by the deconvoluted
spectra in Supplementary Fig. 23 and Supplementary Table 4.
The sequential formation of SEIs under the G route and the direct
formation of SEI under the P-G route were further investigated using
XPS characterization and density functional theory (DFT) calculations
(Supplementary Figs. 24–26 and Supplementary Table 4). We found
that the broad bands appeared in both routes due to the wide
distribution of size and microenvironment of the highly amorphous Li-
SEI. Nevertheless, the directly formed Li-SEI by the P-G route had a
notably reduced thickness compared to the sequentially formed Li-SEI
from the primary Cu-SEI (Supplementary Fig. 24). Moreover, the
organic B–F components from the decomposition of LiDFOB were
present in the sequentially formed SEI; such components were hybri-
dized with inorganic species of LiF with varying amounts across the
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
Raman spectra recorded during the formation and evolution of the SEI under the
P-G route (e). Schematics of the structure and chemistry of the SEI formed under
the P-G route (f). g, h Normalized Raman peak area of bands associated with B–O
and carbonate species in sequentially formed Li-SEI (g) and directly formed Li-SEI
(h). i, j Percentages of specified components in the sequentially formed Li-SEI (i)
and directly formed Li-SEI (j), calculated from the XPS spectra.
SEI, as evidenced by the XPS depth profile (Supplementary Fig. 25).
Under the P-G route, since the electrolyte experience a large driving
force for reduction at the potential below 0 V, DFOB anions can cap-
ture electrons from Li metal to enable the B–O or B–F bond cleavage;
thus low-oxidation-state inorganic species such as LiF (Supplementary
Fig. 25) became the main components throughout the Li-SEI. More
importantly, the sequentially formed Li-SEI contains more organic
species, especially in the outer region occupied by high-oxidation-
state organic species such as ROCO2Li and ROLi (Fig. 3g, i). However,
the directly formed Li-SEI exhibited a distinctive polymeric-like struc-
ture. The vibrations of O–B–O/CH2 at 1295 cm−1 and Li–O/(LiF)n at
470 cm−1 from crosslinked oligomeric borates (e.g., –B(OCH2CH2)3–)
became intensified while carbonate species became weakened
(Fig. 3h, j and Supplementary Fig. 25). Reactions of the electron-
deficient B-containing intermediates from DFOB anion decomposition
with other SEI components (e.g., electron-rich lithium alkoxide or
lithium semicarbonates) could be one of the reasons that leads to the
crosslinking (Supplementary Fig. 26). It is generally acknowledged that
the SEIs with polymeric-like structures are beneficial to suppressing Li
dendrite growth60,61. Such SEIs composed of oligomers incorporated
5
Article https://doi.org/10.1038/s41467-023-39192-z

Conventional understanding vs. Renewed understanding by DS-PERS

Normal: Sequential formation of SEI on Cu and then Li

SEI on Cu overlooked
(involving restructuring)

SEI Inferior Li-SEI

Li Inferior Cu-SEI Li
Cu Cu Cu Cu Cu

Improvement: Direct formation of superior SEI on Li

SEI on Cu unchsnged
(suppressing inferior Cu-SEI)

SEI Superior Li-SEI

SEI Li w/o Cu-SEI Li
Cu Cu Cu Cu Cu Cu

Fig. 4 | Schematics of conventional and renewed understandings of SEIs for- unchanged after Li deposition. The DS-PERS revealed a sequential formation of SEI
mation and evolution. In the conventional understanding, either the SEI forma- on the Cu and then on the Li, with a significant chemical and structural
tion on Cu is overlooked, or the SEI formed on Cu is considered to remain reconstruction.

c f Bulk electrolyte
a Li+ anion solvent
DFOB (ring breathing)
SSIP CIP
Intensity (a.u.)

AGG-I
Metal / SEI / Electrolyte

(74.3%)
AGG-I
SSIP AGG-II
CIP
AGG-II
(16.4%)
(9.3%)

700 710 720 730 740 750 840 860 880 900 920 940
d g Sequential SEI/electrolyte
Free DEC/FEC
Intensity (a.u.)

AGG-I
Li or Cu

SSIP
CIP AGG-II
(14.1%) (4.8%) ROBFC2O4Li, ROCO2Li
b Outer layer of SEI
SEI/electrolyte interface 700 710 720 730 740 750 840 860 880 900 920 940
e Free DEC/FEC
h Direct SEI/electrolyte
Intensity (a.u.)

AGG-I

III III

SEI II II
II II
I
LiF, B-(O-CH2-CH2)n
Cu Outer layer of SEI
700 710 720 730 740 750 840 860 880 900 920 940
Raman shift (cm 1) Raman shift (cm 1)

Fig. 5 | The desovlation of Li-ions at different SEI/electrolyte interfaces revealed
by DS-PERS. a Schematic for Li electrodeposition on the electrode with the SEI. The
solvated ions in the electrolyte need to be desolvated at the SEI/electrolyte inter-
face and then transported through the SEI to the metal/SEI interfaces for reactions.
b Schematic the schematic of the DS-PERS that can in-situ collect the signals from
the SEI/electrolyte interface. The hotspots III enhance the Raman signals from the
SEI/electrolyte interface. c–e Potential-dependent Raman spectra of Li-ion solva-
tion structure at bulk electrolyte (c), sequentially-formed SEI/electrolyte interface
(d) and directly-formed SEI /electrolyte interface (e). f–h Schematics of Li-ion sol-
vation structure governed by the chemical structure of SEIs.

with inorganic species are usually mechanically robust and more facile interface for charge transfer reactions (Fig. 5a). To reveal the roles of
for Li-ion transport. The above information demonstrates that the DS- the SEI/electrolyte interface in regulating the desolvation of Li-ion and
PERS with synergetic LSP enhancements is powerful in elucidating the follow-up Li electrodeposition, DS-PERS was utilized to collect the
different SEI formation mechanisms, and such in-depth understanding enhanced Raman signals from the hotspots III at the SEI/electrolyte
can be truly rewarded by designing the favorable SEI to enable the interface (Fig. 5b).
stable cycling of Li metal batteries (Fig. 4). The Raman spectra of bulk electrolyte (LiDFOB-LiBF4 in DEC-FEC)
are shown in Fig. 5c (left panel). The DFOB anion bands at
Desolvation of Li-ion at SEI/electrolyte interface 700 ~ 750 cm−1 can be deconvoluted into three distinctive bands at 711,
The desolvation of Li ions starts at the SEI/electrolyte interface, fol- 730 and 741 cm−1 associated with solvent-separated ion pairs (SSIPs,
lowed by the Li-ion transport through the SEI to reach the metal/SEI non-coordinated DFOB)/contact ion pairs (CIPs, DFOB coordinating to

Nature Communications | (2023)14:3536 6

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one Li-ion), aggregates-I (AGGs-I, DFOB coordinating to two Li-ions)
and AGGs-II (DFOB coordinating to four Li-ions), respectively (Sup-
plementary Fig. 27). Obviously, the majority of DFOB anions exists as
AGGs-I with small amounts of SSIPs/CIPs and AGGs-II due to the strong
interaction between DFOB and Li+ (Fig. 5f). This is also verified by the
spectra of solvents (Fig. 5c, right panel), where Raman bands from
fewer coordinated solvents to Li+ are observed.
For the interface between the sequentially formed SEI and elec-
trolyte (Fig. 5d), the local solvation structure is different from that in
the bulk electrolyte, where the number of free DFOB anions reduces to
form more AGGs through interactions with multiple Li-ions. We expect
that the outer SEI region consisting of electron-rich species such as
ROCO2Li and ROBFC2O4Li can repel the negatively charged DFOB
anions, leading to the coexistence of SSIPs/CIPs and AGGs at this
interface. However, at the interface between the directly formed SEI
and electrolyte (Fig. 5e), the solvation structure is dominated by AGGs-
I, as reflected by the increase of the intensity of free solvents (largely
weakened interaction with Li+). In this circumstance, inorganic LiF and
crosslinked oligomeric Li–B(OCH2CH2)3–R are the major components
in the outer region. These species have higher interfacial energy that
may modify the Li+ solvation environment through the interfacial
interactions. For example, the LiF tends to bind with C = O and B‒F in
the DFOB anion. DFT calculations show the large binding energies of
the LiF coordinated with C = O (−0.33 eV) and the LiF coordinated with
both C = O and B‒F (−0.39 eV), leading to the significant increase in the
proportion of AGGs-I that has spare C = O and B‒F coordination bonds
to LiF. In summary, the structure and chemistry of SEI, especially in the
outer region, can dramatically affect the Li+-anion interaction at the
SEI/electrolyte interface. The change in the solvation structure of Li-
ions is anticipated to have a significant impact on its desolvation
behavior and consequently alter the Li deposition. It demonstrates
again that the DS-PERS can serve as a powerful tool to reveal the
important roles of SEI/electrolyte interfaces in the Li-ion desolvation
and Li deposition on the Li metal anode.
Improve battery performance with the designed favorable SEIs
We expect that the directly formed SEI and its interfaces are favorable
for the stable Li deposition/dissolution on the Li metal anode. The
improved performance of the electrode with such an SEI is demon-
strated in Fig. 6a–d, where the performance of Cu | |Li cells with Cu
current collectors covered by different SEIs are compared. The elec-
trolyte used here is the LiDFOB-LiBF4 in DEC-FEC.
The cells with directly formed Li-SEI exhibited a long cycle life of
over 200 cycles and an average Coulombic efficiency (CE) as high as
99.5% (Fig. 6a). In addition, the Li deposition overpotential remained
stable without presenting an obvious voltage hysteresis (Fig. 6c, d). In
contrast, the one with the sequentially formed SEI showed a much
shorter cycle life (Fig. 6a) and dramatically varied voltage hysteresis
during cycling (Fig. 6b). Moreover, with directly formed Li-SEI, a uni-
form Li deposit was formed without apparent dendrite and porous
structures (Fig. 6e, f). The cell performance can be further improved by
the periodic application of a higher current density pulse of optimized
magnitude during charge-discharge cycling, leading to the rapid
deposition of Li metal to maintain the high quality of directly formed
SEI. It can be obviously observed that the cell with in-situ restoring
showed more stable cycling with a further boosted CE of 99.6%
(Fig. 6g, h).
We further assessed the potential of engineering the directly
formed SEI to enable the stable cycling of anode-free full-cells. Proof-of-
concept anode-free full cells using the commercial LiNi0.5Mn0.3Co0.2O2
(NMC532) cathode were tested (Fig. 6i, j). For the cell with the directly
formed SEI on the Cu current collector, it delivered the initial discharge
capacity of ~176 mAh g−1, and approximately 80 cycles with a high and
stable CE were achieved at a 0.2 C charge/0.5 C discharge rates before
the capacity fell to 80%, as shown in Supplementary Fig. 28. For the cell
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
with the sequentially formed SEI, considerable performance degrada-
tion was observed. After 20 cycles, the morphology of deposited Li on
the Cu with sequentially formed SEI was dendritic and porous (Fig. 6k).
In contrast, the deposited Li on Cu with the directly formed SEI showed
relatively densely packed and flat grains even after 50 cycles (Fig. 6l).
In summary, we developed a DS-PERS method for in-situ char-
acterization of the formation and evolution of SEI in Li metal batteries.
The synergistic LSP enhancement from nanostructured Cu, SHINs and Li
deposits was utilized to enable bottom-up nondestructive detection of
the structure and chemistry of SEIs and related interfaces with depth
sensitivity. The dynamic molecular-level information of the SEI revealed
that the sequential formation of SEIs on the bare Cu current collector
and then freshly deposited Li is a universal phenomenon in both ether-
based and carbonate-based electrolytes, which is overlooked in the
conventional understanding of SEI formation. Specifically, the primary
SEI formed on Cu is composed of less stable high-oxidation-state com-
ponents and has to undergo chemical restructuring upon subsequent
concurrent Li deposition to complete the formation of a final SEI on Li,
which is less desirable for battery performance. Such a sequential SEI
formation route can be altered by applying an electrochemical strategy
to promote rapid Li deposition and thus suppress the preceding primary
SEI formation on Cu, leading to the direct formation of SEIs on Li with
the enrichment of more stable low-oxidation-state components. This in-
depth understanding of SEI and related interfaces guided us to design a
potentiostatic-galvanostatic polarization strategy for achieving an
improved polymeric-like structured Li-SEI in a dual-salt carbonate-based
electrolyte. The electrodes engineered with this type of SEI exhibited
significantly enhanced cycling stability and an expanded lifetime in the
anode-free Li metal batteries. This study expands the capability of DS-
PERS to study the complicated interfaces/interphases in Li metal bat-
teries, which opens up a new perspective in real-time investigation and
understanding of the mechanisms of SEI formation and evolution and
the roles of SEI in regulating Li-ion desolvation and Li deposition, which
is pivotal in the rational construction of SEIs and related interfaces for
practical batteries including other alkali metal batteries.
Methods
Preparation of nanostructured Cu substrate
The traditional oxidation-reduction cycle (ORC) method was used for
electrochemical roughening of the surface of the Cu substrate to
obtain nanostructures for effective SERS activation54. The ORC treat-
ment was performed in a 0.1 M KCl aqueous solution using a potential
step procedure described as follows: oxidation at 0.4 V for 5 s followed
by reduction at −0.4 V for 5 s, which was repeated for 3 cycles. The
obtained nanostructured Cu substrate was rinsed with deionized water
and rapidly dried under vacuum conditions.
Synthesis and assembly of Au@SiO2 SHINs
Au@SiO2 SHINs were synthesized following previous report44. Au
nanospheres with a diameter of ~60 nm were first prepared using the
sodium citrate reduction method. Then, 200 mL of HAuCl4 aqueous
solution (0.01 wt.%) was heated to boiling under string. A total of
1.6 mL of sodium citrate aqueous solution (1 wt.%) was quickly added
to the above boiling solution and refluxed for 1 h. Then, the sol was
allowed to cool to ambient conditions for the next step. The ultrathin
SiO2 shell was then coated by the high-temperature silicate hydro-
lyzation method. A 400 μL of (3-aminopropyl) trimethoxysilane
(1 mM) was added to 30 mL of the as-prepared Au nanosphere sol
under stirring without heat. After 15 min of stirring at room tempera-
ture, a sodium silicate solution with the pH adjusted to approximately
10.0 by H2SO4 was added and stirred for another 5 min. Then, the
mixture was transferred to a boiling water bath and stirred for
approximately 30 min to coat the pinhole-free SiO2 shell with ca. 2 nm
in thickness. The as-prepared Au@SiO2 nanoparticles were cen-
trifuged thrice and washed with deionized water for later use.
7
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Fig. 6 | Electrochemical performances of anode-free electrodes covered by
different SEIs. a CE of Li deposition/dissolution on Cu electrodes covered by dif-
ferent SEIs (deposition at 0.5 mA cm−2 and dissolution at 1.25 mA cm−2; capacity of
1.5 mAh cm−2). b The hysteresis of Li deposition/stripping for the Cu electrodes
covered by different SEIs. c, d Voltage profiles of the cells with Cu electrodes
covered by sequentially formed SEI (c) and directly formed SEI (d). e, f Cross-
sectional SEM images of Li deposited on the Cu electrodes covered by sequentially
formed SEI (e) and directly formed SEI (f). Scale bar: 10 μm. g, h CE (g) and voltage
For the assembly of Au@SiO2 SHINs on the surface of the
nanostructured Cu substrate, the above concentrated sol was diluted
with 0.5 mL of deionized water to make up a stock solution. Two
microliters of the stock solution were then drop-cast onto the surface
of a freshly nanostructured Cu substrate and rapidly dried under
vacuum overnight.
Characterization of the samples
The morphologies of the nanostructured Cu surface and Au@SiO2
SHINs were characterized by scanning electron microscopy (SEM,
HITACHI S-4800) and high-resolution transmission electron microscopy
(HRTEM, F30) coupled with energy dispersive X-ray spectrometry,
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
profiles (h) of Li deposition/dissolution on Cu electrode covered by directly formed
SEI with periodic in-situ restoring under higher current density (deposition at
5.0 mA cm−2 and dissolution at 5.0 mA cm−2). i, j Capacity retention (i) and voltage
profiles (j) of the coin-type Cu| |NMC532 cells with Cu electrodes covered by dif-
ferent SEIs (charge at 0.2 C and discharge at 0.5 C). k, l SEM images of plated Li
morphology in the Cu| |NMC532 cells with Cu electrodes covered by sequentially
formed SEI (k) and directly formed SEI (l), respectively. Scale bar: 10 μm.
respectively. The distribution of Au@SiO2 SHINs on the nanostructured
Cu substrate after Li deposition as well as the morphology of the Li metal
surfaces after cycling were characterized by SEM (Zeiss GeminiSEM 500)
with an air-isolating transfer apparatus to avoid air exposure of
the samples. XPS measurements were performed on an ESCALAB Xi+
(Thermo Scientific) spectrometer using monochromatic Al Kα
(1486.7 eV) X-ray source at 15 KV with a beam spot size of 650 μm. The
binding energies were referenced to the C 1 s line at 284.6 eV from
adventitious carbon. Depth profiling was fulfilled using Ar ion sputtering
in the x-y scan mode at ion acceleration of a 2 kV and ion beam current
of 2 μA over an area of 2 × 2 mm2. The thickness of the SEI was estimated
based on the calibrated sputtering rate of 5 nm per minute for Ta2O5.
8
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In-situ electrochemical Raman spectroscopy
In-situ Raman measurements were conducted on a Raman-11 system
(Nanophoton) equipped with a 50× (NA 0.45) objective and a 300
grooves/mm grating. A 785 nm laser was used to avoid the fluores-
cence background from the electrolyte (Supplementary Fig. 9). The
homemade sealed Raman cell, in which the nanostructured Cu deco-
rated by SHINs served as the working electrode and Li foils served as
both the reference and counter electrodes, was assembled in an Ar-
filled glovebox (< 0.1 ppm of H2O and O2). The working electrode
surface faced upwards and towards a quartz glass window of the cell
with 0.5 mm thickness. The laser power at electrode was approxi-
mately 0.7 mW μm−2 and the acquisition time was 60 s for each spec-
trum. Raman frequencies were calibrated using a Si wafer. To remove
the interference of fluorescence, the Raman spectra were background-
corrected based on a fifth-order polynomial function. For a higher
signal-to-intensity ratio, while preserving the spectroscopic features, a
peak extraction and retention algorithm62 was applied to the Raman
spectra recorded on bare nanostructured Cu and integrated Cu-SHINs
substrates after Li deposition, as shown in Fig. 2.
Measurements of electrochemical performances
All electrochemical tests were carried out in a 2016-type coin-cell
configuration and all cells were fabricated in an Ar-filled glovebox, with
one layer of Celgard 2325 used as a separator and 50 μL electrolyte.
Galvanostatic charge-discharge cycling was performed on LANHE
CT2001A battery testing system. Two types of SEIs were preformed
on Cu current collectors with Cu | |Li half-cell configurations before
electrochemical testing. The sequentially formed SEI on Cu (19 mm
diameter) was prepared by normal galvanostatic route with cathodic
polarization at 0.5 mA cm−2 for 5 h followed by stripping to 0.5 V at
1.25 mA cm−2. The directly formed SEI on Cu was prepared by
potentiostatic-galvanostatic route, where a potential of −0.1 V was
applied for 100 s in the potentiostatic period and a constant cathodic
current density of 0.5 mA cm−2 was immediately applied for 1 h in
the subsequent galvanostatic period. The residual Li after the
potentiostatic-galvanostatic route was removed by electrochemical
dissolution. For Coulombic efficiency tests, Cu | |Li half-cells were
cycled by depositing 1.5 mAh cm−2 of Li onto the Cu current collector
with different preformed SEIs at −0.5 mA cm−2 followed by stripping to
0.5 V at 1.25 mA cm−2. The Coulombic efficiency was calculated by
dividing the total stripping capacity by the total deposition capacity.
For periodic in-situ restoring strategy, a higher current density pulse of
5 mA cm−2 was applied to Cu | |Li half-cell every 20 normal cycles.
For anode-free full cell tests, Cu | |NMC532 cells were assembled using
a Cu current collector (19 mm diameter) with differently preformed
SEIs as the anode and commercial NMC532 (Easpring) coated on Al foil
(13 mm diameter) as the cathode (94.5 wt.% active). The typical loading
of NMC532 was approximately 15 mg cm−2. Before the measurements,
all the cells were subjected to two formation cycles at C/10 rate for
both charge and discharge processes. These cells were cycled between
3.6 V and 4.5 V at the C/5 rate for charge and the C/2 rate for discharge.
1 C is equal to 170 mA g−1 of active NMC532 materials. For these con-
ditions the areal capacity was about 2.5 mAh cm−2. All electrolytes used
were 0.6 M LiDFOB-0.6 M LiBF4/DEC-FEC (2:1, V/V, anhydrous > 99%,
DoDoChem), and all cells were tested at 25 °C. Each test was repeated
with three coin cells to ensure consistency.
Theoretical simulation and calculation
The simulated electromagnetic field was obtained by commercial
simulation software (COMSOL Multiphysics) based on the finite ele-
ment method. A spherical simulation domain, whose diameter was
1.8 μm, was created, and perfectly matched layers (PMLs) were
employed to simulate an open boundary. The bottom half of the
simulation domain was set as Cu. The medium over the Cu substrate
was set to be the electrolyte or SEI. A quarter of the spherical Cu
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
nanoparticles, whose diameters were 57 or 100 nm, were buried in the
Cu substrate. The size of the nanogap was 2 nm for the adjacent Cu
nanoparticles. The Au core (55 nm)-SiO2 shell (2 nm) nanoparticles
were modelled as core-shell nanoparticles. The minimal mesh size was
0.1 nm in close proximity to the nanoparticles and gradually became
coarser towards the borders of the simulation domain. The refractive
indexes of the electrolyte and the SEI were 1.4 and 1.6, respectively63.
The permittivity for Au, Cu, Li and SiO2 were taken from references64,65.
Density functional theory (DFT) calculations were implemented with
the B3LYP functional66,67 and 6–311 + G(d, p) basis set. The implicit
solvent model (SMD)68 was used with acetone (a dielectric constant of
20.5) as the default solvent to consider the role of solvent effect.
The structures of FEC, DEC, LiDFOB and the corresponding reaction
process as well as DFOB-Li+ coordination were performed by using
Gaussian 09 program package69.
Data availability
The data that support the findings of this study have been included in
the main text and Supplementary Information. All other relevant data
supporting the findings of this study are available from the corre-
sponding authors upon request.
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Acknowledgements
This work was supported by the National Natural Science Foundation of
China (22002129 (Y.G.), 21972119 (B.W.M.), 21991151 (B.W.M.), 22202162
(E.M.Y.), 22072123 (J.W.Y.), 22102137 (W.W.W.)), the China Postdoctoral
Science Foundation (2019TQ0177 (Y.G.), 2022M722648 (E.M.Y.),
2022T150548 (W.W.W.)). We thank H.X. Lin, C.Y. Li, and F.R. Fan for
helpful discussions and advice, Y.H. Hong for experimental assistance
and C. Geng for help on schematic design.
Author contributions
Z.Q.T., B.W.M., and Y.G. conceived idea. Y.G., B.W.M., and Z.Q.T.
designed experiments and analyzed results. Y.G., E.M.Y., B.W.M., Z.Q.T,
Nature Communications | (2023)14:3536
https://doi.org/10.1038/s41467-023-39192-z
C.Y., and R.X. wrote the manuscript. Y.G., J.H.W., R.Y.Z, C.J.Z., G.L., H.Y.L
and W.W.W. performed experiments. E.M.Y. conducted the COMSOL
simulations. J.D.L. conducted the DFT calculations. S.H.L., J.L.Y., Y.Q.,
J.W.Y., D.Y.W., L.Z., G.K.L. and J.F.L. helped with discussion. All authors
discussed and analyzed the data.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information The online version contains
supplementary material available at
https://doi.org/10.1038/s41467-023-39192-z.
Correspondence and requests for materials should be addressed to
Zhong-Qun Tian, Yi Cui or Bing-Wei Mao.
Peer review information Nature Communications thanks Guang Yang
and the other, anonymous, reviewer(s) for their contribution to the peer
review of this work. A peer review file is available.
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